Production of etherg suitable as dis



Patented July 4, 1939 PRODUCTION OF ETHEBS SUITABLE AS DIS- PEN SIN G AGENTS AND OF PREPARATIONS THEREFROM Conrad Schoeller. Ludwigshafen-on-the-Bhine',

and Joseph Nuesslein, l ranhfort-on-the-Maln- Hochst, Ge

rmany, assignors to l. G.1Farbenindustrie Aktiengesellschaft, Frankfort-on-tlie- Main, Germany, a corporation of Germany No Drawing. Original application December 22,

' 1932, Serial No. 648,446.

Divided and this application November 16, 1937, Serial No. 174,820.

lnG

ermany January 2, 1932 5 Claims. (Cl. 260-615) Q It is already known that hydroxyalkyl ethers of polyhydric and lower monohydric alcohols'may be obtained by the action of ethylene oxide on 10 the said alcohols.

We have now found that valuable assistants for the textile and related industries and particularly for the preparation of dispersions are obtained by converting, in known manner, aliphatic mono- 15 hydric alcohols containing at least eight carbon atoms in their molecule into their ethers with dior tri-ethylene glycols. The said products are usually soluble or easily dispersible in water, so

that they may be used as such, but, if a particuo larly high solubility in water be desired, it is advantageous when using them in the textile or related industries to combine them with dispersing agents.

The said ethers of diand tri-ethylene glycols or mixtures thereof are obtained for example in a simple manner by warming alcohols of high molecular weight, as for example octyl, decyl, do-

decyl, cetyl, octodecyl or oleyl alcohols or mixtures thereof, in a pressure-tight vessel with cor- 30 responding amounts of ethylene oxide while employing condensation catalysts, such as surface active substances as for example bleaching earths or active charcoal, strongly acid substances as for example sulphuric or phosphoric acids or sodium 35 or potassium bisulphates, or also strongly alkaline agents such as caustic soda or alkali metal alcoholates.

tween about 80 and about 200 C. If the quan tities of ethylene oxide and of alcohols do not correspond to stoichiometrical proportions, mixtures of 'the ethers may be obtained in which the ethers of ethylene glycol, dior tri-ethylene glycols will prevail. The ethers may also be prepared by etherifying the said alcohols with ethylene glycol or dior tri-ethylene glycols, or for example by causing ethylene halogen hydrins to. act

on the alcohols of high molecular weight. The

, alcohols of high molecular weight may be chosen so from octyl, decyl, undecyl, dodecyl, tetradecyl,

cetyl, octodecyl and undecenyl alcohols. In some cases di-ethers of the alcohols with the glycols may be formed together with the mono-ethers,

which di-ethers, or mixtures thereof with-the 55 mono-ethers, may also serve for the same pur- The temperatures are generally be-' poses as the mono-ethers though the latter are generally preferred.

The products prepared in the said manner ar especially suitable as softening agents for textiles of all kinds, as for example those from artificial silk, cotton, wool, natural silk or hast-fibres or from mixtures thereof because they impart to the treated goods a soft and supple touch. They may also be employed with advantage for greasing wool as well as for dressing any fabrics. In washing, bucking, fulling and dyeing liquors they frequently effect a rapid and uniform penetration of the treatment liquid, especially the ethers of dior tri-ethylene glycols. Their capabilities of employment are considerably enhanced by the fact that they chemically react entirely neutral and, contrasted with soaps and Turkey red oils, give no deposits of insoluble salts even when employed in water containing lime. V

The said ethers may be employed alone or together with other assistants usual in the textile, leather, paper, lacquer, pharmaceutical and cosmetic industries, and in the production of insecticides. For example they may be employed in admixture with soapy substances, such as soaps, Turkey red oils, sulphuric esters or true sulphonic acids of organic compounds of high molecular weight or water-soluble salts of the sulphonated compounds, or in'admixture with glue, gelatine, gum arabic or with organic more or less waterinsoluble solvents, such as carbon tetra-chloride, trichlorethylene, cyclohexanol, cyclohexanone and the phenyl, cresyl or xylyl ethers of ethylene glycol, or the like. They are especially suitable for the preparation of dispersions of oily and fatty substances which are insoluble or only soluble with difficulty in water, such as fats, waxes, aliphatic alcohols of high molecular weight,

'paraflln waxes or mineral oils, the dispersions tion of thin aqueous emulsions it is preferable to employ the said ethers together with the usual dispersing agents, as for example with soaps, Turkey red oils, acid sulphuric esters of aliphatic alcohols of High molecular weightll'such as those stearic sulphonic acid, taurides, such as -oleicl'-.

methyl tauride, (obtainable according to the British Patents Nos. 343,899 and 341,053), sulphonic acids of alkylated aromatic hydrocarbons or the water-soluble salts of these compounds.

- The following examples" will further illustrate the nature of this invention butthe invention is not restricted to these examples. The parts are by weight.

Example 1 1 part of the ether obtainable by heating 1 molecular proportion of dodecyl alcohol and from 2 to 3 molecular proportions of ethylene oxide in a pressure-tight vessel at 160 C. with an addition of a small amount of caustic potash is mixed with 1 part of the sodium salt of the sulphuric ester of hydroxy stearic acid. The resulting oil is soluble in water and is eminently suitable as a wetting or spot removing agent, as well as for scouring wool, as emulsifying agent, or for brightening or dressing textilematerrals.

Example 2 A mixture of 1 part of the ether obtainable by heating for three hours at 140 C. in a pressure-tight vessel 1 molecular proportion of octodecyl alcohol and 2 molecular proportions of ethylene oxide in the presence of sodium ethylate, and 1 part of a 40 per cent aqueous paste of the sodium salt of oleic-N-methyl tauride is slowly diluted with hot water while stirring continually. A stable emulsion is obtained which may be employed with advantage as a softening agent for textiles of all kinds, especially for artificial silk. If desired, the resulting mono-octodecyl ether of di-ethylene glycol may be etherified with dodecyl alcohol, the resulting mixed ether being applicable for the same purpose as the mono-octodecyl ether.

The sodium salt of hydroxy-octodecane sulphonic acid or a highly sulphonated olive or castor oil, such as the sulphuric ester of hydroxystearic acid, may be employed with equal softening effect instead of the oleic-N-methyl tauride.

Example 3 20 parts of paraffin oil, 10parts of hard paraffln wax, 20 parts of petroleum jelly and 10 parts of the product obtained by reacting 2 molecular proportions of ethylene oxide with 1 molecular proportion of dodecyl alcohol in a closed vessel at 160 C., are fused together and 40 parts of water of about 50 to C. are stirred slowly into the mixture. Al homogeneous stable paste is obtained which may be employed for example as a skin cream.

Example 4 2 parts of octodecyl stearate (C1'lm5.cooCl8H3l) while stirring continually, into a solution of 18 parts of water and 2 parts of Marseilles soap, the soap solution being kept at about 60 to 70 C.

ner a homogeneous, stable emulsion is obtained The resulting mass is then diluted with 20 parts '01 water at the same temperature. In'this manwhich may be readily further diluted by the Example 5 l part of the product obtainable by the action of from 2 to 3 molecular proportions of ethylene oxide on 1 molecular proportion of oleyl alcohol is fused with about 6 parts of a solid polymerisation product of ethylene oxide which has been prepared by the polymerisation of ethylene oxide in the presence of caustic alkali as described for .flxample in the U. S. Patent Specification No. 1,921,378. The resulting mixture is suitable, by reason of its protective colloid action, especially as an assistant in dyeing because it prevents the precipitation of calcium soaps and at the same time effects a level dyeing.

Example 6 A printing paste is prepared from 30 parts of Acid Violet 4 BC (Schultz, Farbstofitabellen, 1931, page 339, No. 806), 50 parts of glycerine, 500 parts of British gum in water (1:1), 20 parts of a condensation product from 1 molecular proportion of dodecyl or oleyl alcohol and from 2 to 3 molecular proportions of ethylene oxide and 380 parts of water.

The mixture is warmed for 10 minutes and then 20 parts of ammonium oxalate are added. Wool muslin is printed in the usual manner with the said paste, dried and steamed moist for an hour. A deep and level print is thus obtained even on nonchlorinated wool.

Example 7 3 molecular proportions of gaseous ethylene oxide are introduced at 130 C. into a stirring vessel containing a mixture of 1 molecular proportion of oleyl alcohol with 1 per cent of its weight of caustic soda. An oily product, consisting mainly of the mono-oleyl ether of tri-ethylene glycol, is obtained'which is particularly suitable for the production of aqueous emulsions of waterinsoluble oils and fats, such as olive oil or mineral lubricating oils. If for example olive oil or a mineral lubricating oil is homogeneously mixed with 5 per cent of its weight of the aforesaid ether and the mixture is stirred with 5 times by weightof water, stable emulsions are obtained which can be diluted with any further quantities of water without breaking the emulsion. If fungicidal or insecticidal substances are added at any stage to such mineral oil emulsions valuable compositions for combating plant pests are obtained.

What we claim is:

1. Dispersing, wetting, cleansing and softening agents suitable in the textile and related industries, consisting essentially of an ether of one glycol selected from the group consisting of diethylene glycol and tri-ethylene glycol, one hydroxyl group thereof being etherifled with a saturated aliphatic radicle free from hydroxy groups containing at least 8 carbon atoms.

2. Dispersing, wetting, cleansing and softening agents suitable as assistants in the textile and related industries consisting essentially of an ether of di-ethylene glycol one hydroxyl group thereof being etheriiled with one saturated aliphatic radicle free from hydroxy groups containing at least 8 carbon atoms.

3. Disperslng, wetting, cleansing and softening agents suitable as assistants in the textile and related industries consisting essentially of an ether of tri-ethylene glycol one hydroxyl group thereof being etherified with one saturated aliphatic radicle free from hydroxy groups containing at least 8 carbon atoms.

4. Anether, of dodecyl alcohol with (ll-ethylene glycol suitable for use as a dispersing agent.

5. An ether, of octadecyl alcohol with triethylene glycol suitable for use as a dispersing agent. I

CONRAD SCHOELLER. JOSEPH NUESSLEDL 

